Controlled release fertilizer composition

ABSTRACT

A controlled release fertilizer composition and methods to produce the controlled release fertilizer composition are described. The controlled release fertilizer composition comprises a water soluble fertilizer core that is coated with a polymeric layer, intermediate layer, and a sulfur layer. If desired, the sulfur layer can be coated with an outer water-insoluble layer.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.13/211,021 filed on Aug. 16, 2011, which was a continuation of U.S.application Ser. No. 12/833,560 filed on Jul. 9, 2010, which was acontinuation of U.S. application Ser. No. 12/174,322 filed on Jul. 16,2008, issued as U.S. Pat. No. 7,771,505 on Aug. 10, 2010, all of whichincorporated herein by reference in their entirety.

FIELD OF INVENTION

This invention relates to controlled release fertilizers.

BACKGROUND OF THE INVENTION

Fertilizers have been used for many years to supplement nutrients ingrowing media. In recent years the art has focused on techniques todeliver controlled amounts of plant nutrients to the soil or othergrowing media. It is recognized, for example, that controlling therelease of plant nutrients such as nitrogen from highly solublefertilizer granules is desirable because releasing the nutrients over anextended period of time achieves advantages which include increasedefficiency of fertilizer use by plants, reduced application costs sincefewer applications of fertilizer are required and reduced nutrient losscaused by leaching and denitrification. The coating of sulfur on thesurface of the fertilizer granules may reduce the dissolution rate ofthe granules and impart controlled-release characteristics. In essence,the water in the soil, and rain water are kept away from the verysoluble fertilizer until a granule develops a flaw such as a crack orfissure in the coating, or the coating is penetrated by microbialaction.

Due to the inherent brittleness of the crystalline solid sulfur-coatingwhich forms on the granule, and the thin, or even non-continuous coatingon many of the granules, it is essential that some type of secondaryouter coating or sealant be applied onto the sulfur-coated surface. Thissealant conventionally is either a polymeric hydrocarbon,petroleum-based wax, or a combination of high viscosity polymericparaffinic oil plus polyethylene, which is spray applied as a hot meltliquid onto the hot, but solidified sulfur-coating surface. Althoughthese sulfur coated fertilizers have received substantial uses, thereare problems from the standpoint of obtaining uniform coatingthicknesses, predictable release characteristics resulting from cracksin the sulfur coatings, essential abrasion and impact resistance, andthe complexity of the processing steps.

More recently, because of problems associated with sulfur coatedfertilizers, such as above defined, polymer coated fertilizers havereceived substantial attention, particularly in view of the improvedcontrolled release properties obtained with certain polymer coatedfertilizers at lower coat weights.

U.S. Pat. No. 5,538,531 (Hudson) teaches a controlled release,particulate fertilizer product having a water soluble fertilizer centralmass encased in a plurality of water insoluble, abrasion resistantcoatings. At least one inner coating is a urethane reaction productderived from reacting recited isocyanates and polyols. The outer coatingis formed from an organic wax.

U.S. Pat. No. 6,358,296 (Markusch et al.) teaches a slow-releasepolyurethane encapsulated fertilizer using oleo polyol(s). U.S. Pat. No.5,851,261 (Markusch et al.) provides a process for the production ofpolyurea encapsulated fertilizer particles comprising applying anisocyanate-reactive component containing at least two amine groups tothe fertilizer particles, and applying a polyisocyanate to the aminecoated particles to form polyurea coated particles.

Sulfur containing isocyanate compositions and a process for theproduction of encapsulated fertilizer compositions are described in U.S.Pat. No. 6,152,981 (Markusch et al). The fertilizer compositions areprepared by applying a mixture of sulfur and an isocyanate to thefertilizer and then applying an isocyanate-reactive material. U.S. Pat.No. 5,599,374 (Detrick) describes a fertilizer composition wherein asulfur coating is applied to a fertilizer core, and thereafter a polymercoating is applied over the sulfur.

U.S. Pat. No. 6,231,633 (Hirano et al.) teaches a granular fertilizercoated with a thermosetting resin coating that may be urethane and ahydrophobic compound, which may be wax. U.S. Pat. No. 6,663,686 (Geigeret al.) teaches a slow-release polyurethane encapsulated fertilizerusing polyurethane and wax.

It is also known in the art to pre-coat particulate plant nutrient withorganic oil and particles as a means to improve the release profiles ofthe particulate plant nutrient (U.S. Pat. No. 6,039,781; Goertz et al.).

U.S. Pat. No. 6,338,746 (Detrick et al.) describes a process of firstcoating a fertilizer with a polymer, then coating the polymer withsulfur and thereafter applying a polymer coating. The polymers aredescribed in U.S. Pat. Nos. 4,711,659 (Moore), 4,804,403 (Moore) and5,374,292 (Detrick). These polymers require that the substrate containsa minimum quantity of reactive —NH₂ groups. Thus, these are notapplicable to all fertilizer compositions for which slow releaseproperties may be desirable.

Although polymer coated fertilizers as above described have receivedsubstantial attention, they are expensive to manufacture. There is aneed in the art to provide controlled released fertilizer formulationsthat are abrasion resistant, and that reduce the cost of fertilizerproduction.

SUMMARY OF THE INVENTION

The present invention relates to controlled release fertilizer.

The present invention provides a controlled release fertilizercomposition that comprises a water-soluble central core of a plantnutrient compound in particulate form, a polymer coating on the plantnutrient, an intermediate layer (IL) on the layer of polymer, and alayer of elemental sulfur on the intermediate layer. The controlledrelease fertilizer composition may include an outer-water insolublelayer on the layer of elemental sulfur. The central core plant nutrientmay be urea. The polymer layer may be a thermoset polymeric layer. Theintermediate layer and the outer water-insoluble layer may be the sameor different, and be selected from the group consisting of a petroleumproduct, a wax, a paraffin oil, a bitumen, an asphalt, a lubricant, acoal product, an oil, canola oil, soybean oil, coconut oil, linseed oil,tung oil, vegetable wax, animal fat, animal wax, a forest product, talloil, modified tall oil, tall oil pitch, pine tar, a synthetic oil, asynthetic wax, a synthetic lubricant, an ethylene-vinyl acetatecopolymer, an ethylene-acrylic acid copolymer; an ethylene-ethylacrylate copolymer, an ethylene-vinyl alcohol copolymer, ethylene-vinyl,alcohol-vinyl acetate terpolymers, a surfactant, soap and a combinationthereof.

The present invention also provides a controlled release fertilizercomposition as described above, that comprises the plant nutrientcompound of from about 37% N to about 44% N on a weight basis, thepolymer layer of from about 1.2% to about 3.0% on a weight basis, theintermediate layer of from about 0.1 to about 0.8% on a weight basis,and the layer of elemental sulfur of from about 1.7% to about 15% on aweight basis. Furthermore, if the controlled release fertilizercomposition comprises an outer water insoluble layer, then this layercomprises from about 0.1 to about 0.8% by weight.

The present invention also relates to a method of producing a controlledrelease fertilizer composition that comprises, coating a plant nutrientcompound with two or more than two precursor compounds reactive to forma polymer, applying an intermediate layer onto the polymer, and sprayingmolten sulfur onto the intermediate layer to form a sulfur layer. Anouter water insoluble layer may be applied over the sulfur layer. Thepolymer may be a thermoset polymer, and the step of coating the plantnutrient compound with two or more than two precursor compounds reactiveto form a polymer may be at a temperature sufficient to thermoset thepolymer.

The present invention pertains to the process as described above, thatcomprises the plant nutrient compound of from about 37% N to about 44% Non a weight basis, the polymer layer of from about 1.2% to about 3.0% ona weight basis, the intermediate layer of from about 0.1 to about 0.8%on a weight basis, and the layer of elemental sulfur of from about 1.7%to about 15% on a weight basis. Furthermore, if the controlled releasefertilizer composition comprises an outer, water-insoluble layer, thenthis layer comprises from about 0.1 to about 0.8% by weight The polymerlayer may be a thermoset polymeric layer.

The controlled release fertilizers described herein exhibit impact andabrasion resistance, are manufactured at low cost, and undergocontrolled release of the fertilizer core in a manner consistent withthe requirements within the industry for a controlled release fertilizercomposition, and similar to controlled release formulationcharacteristics as known in the prior art. By removing the outer layerof a thermoset polymer as described in the prior art (for example U.S.Pat. No. 6,338,746), and by utilizing a thermoset polymer coating on theinnermost layer that coats the fertilizer core, a lower amount of theprecursor monomer compounds that are required to form the thermosetpolymer layer is required. Furthermore, the combination of one or morethan one intermediate layer in combination with the sulfur layer thatcoats a polymer layer, ensures that the amount of polymer coating can bereduced. The intermediate layer component and the sulfur are relativelyinexpensive compared to the polymer coating. This provides a significantsaving in the costs associated with producing the controlled releasefertilizer composition, and permits an increase in the amount offertilizer component, on a weight basis, present in the final fertilizercomposition. Compositions comprising 37% N to 44% N, and having desiredcontrolled release properties, can be obtained using the methodsdescribed herein.

Furthermore, fertilizer compositions of the prior art that comprise apolymeric outer coat require an amount of set or cure time of thepolymeric layer prior to handling and packaging the fertilizer. Thisrequires a step of storing the fertilizer composition followingmanufacture and prior to packaging. After the outer polymeric layer isset, then the fertilizer composition may be packaged. By removing theouter polymeric coating layer, the fertilizer composition of the presentinvention can be packaged following production, and does not require astep of setting or curing the outer coat. Therefore, the controlledreleased fertilizer composition, and the methods to produce thisfertilizer, as described herein, increase production efficiency.

This summary of the invention does not necessarily describe all featuresof the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features of the invention will become more apparent fromthe following description in which reference is made to the appendeddrawings wherein:

FIGS. 1A and 1B show a time course of fertilizer release. FIG. 1A showsthe release of several examples of fertilizer compositions prior to animpact test. FIG. 1B shows the release of several examples of fertilizercompositions after the impact test

DETAILED DESCRIPTION

This invention relates to controlled release fertilizers.

The present invention relates to a controlled release fertilizercomposition comprising a particulate plant nutrient surrounded by aseries of coatings comprising in series from the inside out, a polymerlayer, an intermediate layer (IL), a sulfur layer and if desired, anouter water-insoluble layer.

The choice of particulate plant nutrient material useful for the presentcontrolled release fertilizer material is not to be restricted. Thepresent fertilizer material has been described primarily with referenceto urea as the plant nutrient. As will be apparent to one skilled in theart, however, other nutrients, including micronutrients can be used toprepare the controlled release fertilizer compositions in accordancewith the present invention. For example, the plant nutrient material maybe selected from the group consisting of nitrogen, phosphorus,potassium, sulfur, micronutrients and mixtures thereof. Other fertilizermaterials can be utilized, for example, but not limited to ammoniumphosphate, ammonium sulfate and mixtures thereof or granule mixture ofbasic fertilizer materials. Non-limiting examples of usefulmicronutrients may be selected from the group comprising of copper,zinc, boron, manganese, iron and mixtures thereof.

Urea is characterized as having functional reactive groups at thesurface of the urea which may be used to react with a diisocyanate whenforming the polymer layer. This reaction causes the polymer layer to bechemically bonded to the urea. However, according to the presentinvention, it is not required that the polymer layer be bonded to theurea material.

The amount of fertilizer present within the controlled releasefertilizer composition as describe herein may vary from about 37% N toabout 45% N, by weight, or any amount therebetween, based on the weightof the fertilizer composition, for example 37% N, 38% N, 39% N, 40% N,41% N, 42% N, 43% N, 44% N, by weight, or any amount there between,based on the weight of the fertilizer composition. Using the componentsof the controlled release fertilizer composition and the method toproduce the controlled release fertilizer as described herein, highyielding fertilizers have been routinely produced comprising 42% N to43% N nitrogen (N).

The fertilizer core of the controlled release fertilizer composition ofthe present invention is coated with a polymeric coating. Examples ofpolymeric coatings (see Concise Encyclopedia of Chemical Technology(CECT), Wiley InterScience, 1985) include polyurethane or coatingscomprising polyesters such as alkyd (pp. 70-71 of CECT), or a modifiedalkyd resin (pp. 70-71 of CECT), epoxy resins (pp. 431-433 of CECT),aminoplastic resins (pp. 90-91 of CECT), ureaformaldehyde thermosets(pp. 9-92 of CECT, melamine-formaldehyde thermosets (pp. 90 of CECT),phenolic thermosets (pp. 867-868 of CECT), polyimide thermosets (pp.932-933 of CECT), unsaturated polyester thermosets (pp. 926-927 of CECT)and mixtures thereof. The polymeric coating can be a thermosettingpolymeric coating.

The polymeric layer of the controlled release fertilizer of the presentinvention may for example be a polyurethane, and this coating may beproduced using two or more than two precursor compounds. For example,one of the precursor compounds may be an isocyanate, for example adiisocyanate, or a polyisocyanate. A non-limiting example of adiisocyanate is polymeric MDI (4,4 diphenylmethane diisocyanate),however, other poly-functional isocyanates can be utilized as describedin U.S. Pat. No. 4,804,403 (Moore; see for example Column 8, line 64 toColumn 9, line 27 and Example 1; which is incorporated herein byreference), and include aliphatic, aromatic, and aliphatic aromaticpolyisocyanates. Isocyanates contain two or more —NCO groups availablefor reaction and, as known to one skilled in the art, are widely used inthe production of urethane polymers. Non-limiting examples of suitableisocyanates include: 1,6-hexamethylene diisocyanate, 1,4-butylenediisocyanate, furfuryurylidene diisocyanate, 2,4-toluene diisocyanate,2,6-toluene diisocyanate, 2,4′-diphenylmethane diisocyanate,4,4′-diphenylmethane diisocyanate, 4,4′-diphenylpropane diisocyanate,4,4′-diphenyl-3,3′-dimethyl methane diisocyanate, 1,5-naphthalenediisocyanate, 1-methyl-2,4-diisocyanate-5-chlorobenzene,2,4-diisocyanato-s-triazine, 1-methyl-2,4-diisocyanato cyclohexane,p-phenylene diisocyanate, m-phenylene diisocyanate, 1,4-naphthalenediisocyanate, dianisidine diisocyanate, bitoluene diisocyanate,1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate,bis-(4-isocyanatophenyl)methane,bis-(3-methyl-4-isocyanatophenyl)methane, polymethylene polyphenylpolyisocyanates and mixtures thereof.

The second of the two or more than two precursor compounds used to formthe polymeric coating as described herein, may include a polyol, forexample as described in U.S. Pat. No. 4,804,403 (Moore; see for example;Column 9, lines 3-20, and example 1 which is incorporated herein byreference). Non limiting examples of a polyol include diethylene glycolpolyol, ethylene glycol, polypropylene glycol, organic polyols, forexample as described in U.S. Pat. No. 4,804,403 (Moore; which isincorporated herein by reference), orthophathalate diethylene glycolbased polyester polyols, terephthalate-diethylene glycol based polyesterpolyols, castor oil and oils modified to contain amine or OH groups, forexample modified tong oil, soybean oil, canola oil, sunflower oil,linseed oil, (e.g. U.S. Pat. No. 6,364,925 see for example Markusch etal; see for example Column 8 line 39 to Column 9, line 27 and theexamples; and U.S. Pat. No. 6,358,296, Markusch et al, see for exampleColumn 9 lines 1 to 13, and the examples; which are incorporated hereinby reference), oleo-polyols, for example an epoxidized castor oil,epoxidized sunflower oil, epoxidized linseed oil as described in U.S.Pat. No. 6,358,296 (Markusch et al.; which is incorporated herein byreference), polyether polyols, castor oil derivatives for examplepartial hydrolysates of castor oil, by reacting castor oil with a polyolselected from diols (e.g. ethylene glycol, propylene glycol,1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol,dipropylene glycol, polyethylene glycol, and polypropylene glycol),glycerol, trimethylolpropane, and polyether polyol, or esters formed byreactions between ricinoleic acid and the polyol selected from thesecompounds as described in U.S. Pat. No. 6,176,891 (Komoriya et al.; seefor example Column 7, lines 4 to 16, Column 8, lines 49 to 62; which isincorporated herein by reference), or combinations thereof.

It is not required that the polymer coating as used herein be based onan isocyanate or polyol. The polymer can be virtually any polymer whichis thermoset and which can be applied to the plant nutrient and providea controlled release characteristic, or a portion of the controlledrelease characteristic to the fertilizer composition.

The polymer coating that surrounds the plant nutrient material ispresent in an amount in the range of from about 0.5% to about 3.0% byweight, or any amount therebetween, of the final fertilizer composition.For example, the polymeric coating may comprise from about 0.5% to about2.5% by weight, or any amount therebetween, of the final fertilizercomposition, from about 1.2 to about 1.8% by weight, or any amounttherebetween, based on the weight of the fertilizer composition, or fromabout 0.5, 0.7, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0%by weight, or any amount therebetween, based on the weight of thefertilizer composition.

The polymer coating as described above is coated with a material thatfacilitates the application of sulfur. This coating is herein referredto as intermediate layer (IL). Preferred materials that may be used forthe intermediate layer include but is not limited to a petroleumproduct, a wax, a paraffin oil, a bitumen, an asphalt, a lubricant, acoal product, an oil, canola oil, soybean oil, coconut oil, linseed oil,tung oil, vegetable wax, animal fat, animal wax, a forest product, talloil, modified tall oil, tall oil pitch, pine tar, a synthetic oil, asynthetic wax, a synthetic lubricant, an ethylene-vinyl acetatecopolymer, an ethylene-acrylic acid copolymer; an ethylene-ethylacrylate copolymer, an ethylene-vinyl alcohol copolymer, ethylene-vinylalcohol-vinyl acetate terpolymers, a surfactant, a soap and acombination thereof.

The polymer coat and intermediate layer may be applied as a pre-mixture,for example as described in U.S. Pat. No. 6,663,686 (which isincorporated herein by reference; see Columns 2-6), prior to theaddition of the sulfur layer. In this example, the wax component of thepolymer—wax pre-mixture may comprise from about 10 to about 60 wt % (ofthe total combination of polymer and wax) or any amount therebetween, ofthe polymer-wax pre-mixture, for example 40-60 wt % (of the totalcombination of polymer and wax), or any amount therebetween or 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60 wt % (of the total combination ofpolymer and wax), or any amount therebetween.

If the fertilizer composition is to comprise an outer, water-insolublelayer then the inner intermediate layer, and the outer water-insolublelayer may comprise the same or different components.

If a wax is used for the intermediate layer, the outer water-insolublelayer, or both the intermediate layer and the outer water-insolublelayer, then the wax may be a single type of wax or a mixture ofdifferent waxes. For example, the wax may be selected from anintermediate petroleum wax, an alpha olefin wax, a polyethylene wax, aparaffin wax, a silicon wax, a slack wax, a microcrystalline wax, and anatural wax. Non limiting waxes that may be used in the compositions ofthe controlled release fertilizer of the present invention include thosedescribed in U.S. Pat. No. 5,538,531 (Hudson; see for example Column 5,lines 13 to 27 and the examples; which is incorporated herein byreference). The wax may comprise a drop melting point temperature ofbetween about 60° C. and 80° C., or any temperature therebetween, forexample 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80° C., or anytemperature therebetween.

The intermediate layer that surrounds the polymer coated plant nutrientmaterial may be present in an amount in the range of from about 0.1% toabout 1.0%, or any amount therebetween, based on the weight of thefertilizer composition. For example, the water-insoluble layer may bepresent from about 0.2 to about 0.5% or any amount therebetween, basedon the weight of the fertilizer composition, or from 0.1, 0.2, 0.4, 0.6,0.8, 1.0% or any amount therebetween, based on the weight of thefertilizer composition. A non limiting example of the amount of theintermediate layer is about 0.3% by weight of the fertilizercomposition, in this example, the intermediate layer may be anintermediate petroleum wax. However, an oil, a grease, a wax, or a blendthereof may be used as indicated above.

The intermediate layer may be applied to the polymer coated fertilizerwhile the fertilizer core and the polymer coating is still hot, forexample from about 120° F. to about 250° F., or any temperaturetherebetween. As this temperature is above the melting point for some ofcomponents that may be used for the intermediate layer, the intermediatelayer may form a coating around the polymeric layer in a liquid state.The thickness and amount of the intermediate layer on the polymer coatmay be modified by the amount of intermediate layer applied, and bycontrolling the temperature of the fertilizer core and the polymercoated core.

The intermediate layer material, the outer water insoluble layermaterial, or both the intermediate layer material and the outer waterinsoluble layer material, may be selected from the group of a petroleumproduct, for example but not limited to wax, for example but not limitedto a petroleum wax, paraffin oil, bitumen, asphalt, lubricants and acombination thereof. The intermediate layer may also be selected fromthe group including but not limited to a coal product, a coal-derivedoil, a coal-derived lubricant, a coal-derived bitumen, a coal-derivedwax, and a combination thereof, or a natural product for example but notlimited to vegetable oil, for example but not limited to, canola oil,soybean oil, coconut oil, sunflower oil, castor oil, linseed oil, tungoil, vegetable wax, animal fat, animal wax, a forest product, such astall oil, modified tall oil, tall oil pitch, pine tar and combinationsthereof. Synthetic products for example but not limited to syntheticoils, synthetic waxes, synthetic lubricants, and combinations thereofmay also be used for an intermediate layer. Mixtures of materials fromtwo or more classes listed above may also be used, for example apetroleum product, a coal product, a natural product, a syntheticproduct and a combination of these materials. Furthermore, the materialmay be available as by-products from an industrial process. Theintermediate layer material of the present—fertilizer may also beselected from a soap, a surfactant, or a combination thereof.

Without wishing to be bound by theory, the intermediate layer may act asa lubricant when applying the sulfur layer. The use of an intermediatelayer may ensure an even coating of sulfur during production of thecontrolled release fertilizer composition, and may minimize the amountof sulfur that needs to be applied to the controlled release fertilizercomposition. Therefore, materials that function in a lubricatingcapacity may be used as a component of the intermediate layer.

As noted above, the intermediate layer material may be oil, a wax and anoil in combination, or another lubricating agent in combination with awax, an oil, or a combination thereof. If an oil is to be used, eitheralone or in combination with a wax or other lubricant, then it ispreferred that the oil be in a liquid state from about 120° F. to about250° F., or any temperature therebetween, for example 120, 125, 130,135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200,205, 210, 215, 220, 225, 230, 240, 245, 250° C., or any temperaturetherebetween.

If an outer, water-insoluble layer is used to surround the sulfur layer,then the outer, water-insoluble layer is present in an amount of fromabout 0.1% to about 1.5%, or any amount therebetween, based on theweight of the fertilizer composition. For example, the water-insolublelayer may be present from about 0.2 to about 0.8% or any amounttherebetween, based on the weight of the fertilizer composition, or from0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.5% or any amount therebetween,based on the weight of the fertilizer composition.

A non limiting example of the amount of the water-insoluble layer isabout 0.5% by weight of the fertilizer composition, in this example, thewater-insoluble layer may be an intermediate petroleum wax. The wax maycomprise a drop melting point temperature of between about 60° C. and80° C., or any temperature therebetween. For example, 60, 62, 64, 66,68, 70, 72, 74, 76, 78, 80° C., or any temperature therebetween.

The outer water-insoluble layer may be used to minimize the amount ofsulfur dust that is produced during handling of the controlled releasefertilizer composition. The water-insoluble layer also increases theabrasion resistance of the fertilizer composition, and functions incontrolling the release of the fertilizer within the controlled releasefertilizer composition when the fertilizer composition is exposed towater. The outer water-insoluble layer may act as a hydrophobic layerwhich protects moisture from entering cracks in the sulfur coating.

The outer water-insoluble layer should contain less than about 5% oil,in order to ensure that the layer hardens appropriately to facilitateproper handling of the final fertilizer product.

The sulfur layer surrounds the wax coating of the polymer coated plantnutrient material, in an amount in the range of from about 1.7% to about15%, or any amount therebetween, based on the weight of the fertilizercomposition. For example the sulfur coating may comprise from about 2%to 4%, or any amount therebetween, based on the weight of the fertilizercomposition, from about 2.2% to 3.8%, or any amount therebetween, basedon the weight of the fertilizer composition, or from about 1.7, 1.9,2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6,4.8, 5.0, 5.2, 5.4, 5.6, 5.8, 6.0, 6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4,7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8, 10.0, 10.2,10.4, 10.6, 10.8, 11.0, 11.2, 11.4, 11.6, 11.8, 12.0, 12.2, 12.4, 12.6,12.8, 13.0, 13.2, 13.4, 13.6, 13.8, 14.0, 14.2, 14.4, 14.6, 14.8, 15%,or any amount therebetween, based on the weight of the fertilizercomposition.

Therefore, the present invention provides a controlled releasefertilizer composition that comprises a plant nutrient compound of fromabout 37% N to about 44% N on a weight basis, a polymer layer of fromabout 1.2% to about 3.0% on a weight basis, an intermediate layer offrom about 0.1 to about 0.8% on a weight basis, and the layer ofelemental sulfur of from about 1.7% to about 15% on a weight basis. Thecontrolled release fertilizer composition may also comprise an outer,water-insoluble layer of from about 0.1 to about 0.8% by weight.

The present invention also provides a method of producing a controlledrelease fertilizer composition that comprises, coating a plant nutrientcompound with two or more than two precursor compounds that react toform a polymer, applying an intermediate layer onto the polymer, andspraying molten sulfur onto the intermediate layer to form a sulfurlayer. An outer, water-insoluble layer may be applied over the sulfurlayer. If the polymer is a thermosetting polymer, then the polymer iscoated at a temperature sufficient to form a thermoset polymer.

The controlled release fertilizer composition may be produced using afirst rotating drum comprising precursor components to produce a polymerlayer over top of fertilizer granules. In this procedure, fertilizergranules, having a size range from about 1.0 mm to about 3.0 mm, or anysize therebetween, for example about 1.5 mm to about 2 0 mm or any sizetherebetween, for example 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.2, 2.4,2.5, 2.6, 2.8, 3.0 mm or any size therebetween, are fed from a storagearea, onto a conveyor and fed into a rotating drum, or a pre-heater. Ifa drum is used, in a first section of the rotating drum, the fertilizergranules, may be preheated to about a temperature between 120° F. and250° F., or any temperature therebetween, for example from about 150° F.to about 200° F., or about 120, 125, 130, 135, 140, 145, 150, 155, 160,165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 220, 240, 230, 240,250° F., or any amount therebetween, for example about 170° F. Theheated granules are then coated separately with precursor compounds toproduce the polymer coating. For example if the polymer is a thermosetpolymer, then polymeric MDI (4,4 diphenylmethane diisocyanate), and amixture of TEA (triethanolamine) and DEG (diethylene glycol)polyols, areblended and applied to the fertilizer granules, and the polymercomponents polymerize on the surface of the granules to form a polymercoating.

In a second coating step the polymer coated granules are brought intocontact with am intermediate layer material for example but not limitedto a wax, an oil, a grease, or a combination thereof, at a temperatureof about 120° F. to about 250° F., or any temperature therebetween, forexample from about 150° F. to about 200° F., about 170° F., or about120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185,190, 195, 200, 205, 210, 220, 240, 230, 240, 250° F., or any amounttherebetween, for example about 160° F., which is applied onto thepolymer coated granule.

The polymer and intermediate layer-coated urea is withdrawn from thefirst drum onto a conveyor and fed to a conveyor leading into a secondrotating drum In a continuous process, the coated granules are thenbrought into contact with molten sulfur at a temperature of from about240° F. to about 310° F., or any temperature therebetween, for examplefrom about 240, 250, 260, 270, 280, 290, 300, 310° F., or any amounttherebetween, for example about 290° F. which is sprayed over top of theintermediate layer coating of the polymer coated granule. The moltensulfur forms a solid sulfur layer over the intermediate layer.

If desired, an outer, water-insoluble coating may be applied onto thepolymer coated granule through nozzles within the second drum. Theouter, water-insoluble layer, for example a wax may be applied at atemperature of about 120° F. to about 250° F., or any temperaturetherebetween, for example from about 150° F. to about 200° F., about170° F., or about 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170,175, 180, 185, 190, 195, 200, 205, 210, 220, 240, 230, 240, 250° F., orany amount therebetween, for example about 160° F.

The present invention therefore provides a process for producing acontrolled release fertilizer composition comprising coating a plantnutrient compound with two or more than two precursor compounds thatreact to form a polymer comprising from about 1.2% to about 3.0% on aweight basis, applying a component or composition onto the polymer toform an intermediate layer of from about 0.1 to about 0.8% on a weightbasis, and spraying molten sulfur of from about 1.7% to about 15% on aweight basis onto the intermediate layer to form a sulfur layer. Theplant nutrient composition is from about 37% N to about 44% N on aweight basis of the total ingredients of the controlled releasefertilizer composition. If desired, an outer water-insoluble layer maybe applied over the sulfur layer comprising from about 0.1 to about 0.8%by weight. If the polymer is a thermosetting polymer, then the polymeris coated at a temperature sufficient to form a thermoset polymer.

The release rate and durability of the controlled release fertilizercomposition as described herein may be determined for example, followingan Impact Test or other test used to determine the integrity of thecoated fertilizer product. The impact test may involve dropping forexample, 60 grams of the coated product through a 20 foot long, 3-6 inchdiameter tube onto a metal plate, followed by determining the releaserate of the fertilizer component from the abraded fertilizer product. Todetermine the aqueous release rate, about 10-20 grams of the abradedfertilizer are placed in 150-200 ml of water, and samples are drawn atdifferent time intervals—for example, at 2 hours, 1 day, 3 days 7 days,14 days and 21 days, and the sample tested using an appropriate test forthe fertilizer material. For example, in the case of a urea-basedfertilizer, urea and ammoniacal nitrogen of the sample may be determinedusing any suitable test, for example, the methods outlined by theAssociation of Official Analytical Chemists (AOAC).

Results from such testing demonstrate that the controlled releasefertilizer composition of the present invention comprising, in series, apolyurethane layer that surrounds the fertilizer core, and having forexample 1.8% by weight of the total weight of the fertilizercomposition, a wax coat (0.3% by weight), a sulfur coat (3.8% by weight)which is coated with a wax layer (0.5% by weight; see product 43N-1.8PU-0.3W-3.8S-0.5W, produced according to Example 3, Table 1, andFIGS. 1A, and 1B) provides effective time release of the fertilizercomponent when compared to prior art controlled release compositionscomprising in series, a sulfurlayer that surrounds the fertilizer core(5% by weight of the total weight of the fertilizer composition), apolyurethane layer (2.8% by weight) and a wax coat (0.5% by weight seethe product produced according to Example 1, 42N-5S-2.8PU-0.5W; Table 1,and FIGS. 1A and 1B). Increasing the amount of polyurethane on a %weight basis from 1.8% to 2.5% (see the Product described in Example 4;43N-2.5PU-0.3W-3.8S-0.5W; Table 1 and FIGS. 1A and 1B), furtherdecreases the rate of release of nitrogen from the fertilizercomposition.

Analysis of the costs associated with produced the controlled releasefertilizer of the present invention, for example the product describedin Example 3 (see Table 1; 43 N-1.8PU-0.3W-3.8S-0.5W; and FIGS. 1, and2) indicate a significant cost saving, when compared with the product asdescribed in Example 1 (see Table 1; 42 N-SS-2.8PU-0.5W; FIGS. 1 and 2),or with other controlled fertilizer release properties with a polymercoating that surrounds the fertilizer core and the exterior of thesulfur coating for example, as described in U.S. Pat. No. 6,338,746. Acontrolled release fertilizer composition such as that described inExample 3 of the present invention, (43 N1.8PU-0.3W-3.8S-0.5W) has acost index of: 8.63, compared with a cost index of 9.58 for the priorart product described in Example 1 (42 N-5S-2.8PU-0.5W). Where the costindex is determined by calculating the cost to produce the controlledrelease fertilizer (including the cost of each component, and productionand handling costs to manufacture the product) per unit nitrogen withinthe fertilizer product.

The cost index may be further reduced by reducing the amount of polymerused in the polymer layer, while still maintaining desired releaseproperties. For example a product comprising 1.2% polyurethane has acost index of 8.43. Controlled release fertilizer product comprising2.8% polyurethane (for example the product described in Example 4;(43N-2.8PU-0.3W-2.2S-0.5W) also exhibits a lower cost index (9.43) whencompared to prior art (Example 1; 42N-5S-2.8PU-0.5W) that has a costindex of 9.58.

The controlled released fertilizer of the present invention will beillustrated with reference to the following examples.

The controlled release fertilizer compositions of the following exampleswere prepared essentially as described in U.S. Pat. No. 5,599,374 (seefor example Column 5, line 21 to Column 6 line 33; which is incorporatedherein by reference) but this method was modified to apply the coatingsin the order as described in the examples. The method essentiallyinvolves preheating urea granules (size range from about 1.0 to about3.0 mm) with hot air to about 160° F. to about 180° F., and coating theheated granules with the desired combination of components using aseries of application nozzles within one or more drums

If a polyurethane coating is to be applied (as in Examples 2, 3 and 4),the heated granules are coated with precursor compounds to produce thepolymer coating. For example, a mixture of polymeric MDI (4,4diphenylmethane diisocyanate), TEA (triethanolamine) and DEG (diethyleneglycol)polyols are applied to the fertilizer granules, and the polymercomponents polymerize on the surface of the granules to form the polymercoating.

If the polymer coating is covered with a wax layer (as in Examples 3 and4), then the polymer coated granules are brought into contact with thewax at a temperature of about 120° F. to about 250° F., for exampleabout 160° F., and the wax is applied onto the polymer coated granule.The wax-polymer coated urea is then withdrawn from the first drum andconveyed to a second rotating drum and brought into contact with moltensulfur at a temperature of from about 280° F. to about 310° F., forexample about 290° F. which is sprayed over top of the wax coating. Asecond wax coating is applied to the sulfur coated granule usingapplication nozzles within the second drum and applied at a temperatureof about 120° F. to about 250° F., for example about 160° F.

If the fertilizer core is first coated with a sulfur layer (as inExample 1), then molten sulfur is applied to the heated fertilizergranule at a temperature of approximately 280°-310° F. The sulfur-coatedurea granules then are transferred into a second rotating drum andcoated with precursor compounds to produce the polymer coating includinga mixture of polymeric MDI (4,4 diphenylmethane diisocyanate), TEA(triethanolamine) and DEG (diethylene glycol)polyols which is applied tothe fertilizer granules, and the polymer components polymerize on thesurface of the granules to form the polymer coating. The polymer coatedgranule is then coated with a wax layer at a temperature of about 120°F. to about 250° F., for example about 160° F.

If the fertilizer core is coated with polyurethane, and sulfur (as inExample 2), then the polyurethane coated fertilizer granule is coatedwith a sulfur layer at a temperature of approximately 280°-310° F. Thesulfur-coated urea granules are then coated with a layer of wax usingapplication nozzles within the second drum and applied at a temperatureof about 120° F. to about 250° F., for example about 160° F.

The fertilizer compositions as produced above may then be cooled withcool air to a temperature in the range of about 95° F. to about 115° F.,for example using a fluid bed cooler. The granules may then be sized,stored, and packaged.

EXAMPLES Example 1 42N-5S-2.8PU-0.5W (Comparative Example)

In this Example, a controlled release fertilizer material was preparedaccording to the teachings of U.S. Pat. No. 5,599,374 by Detrick (seefor example Column 2 line 65 to Column 3, line 22; which is incorporatedherein by reference), with addition of an external wax layer applied asdescribed above. The urea granule (91.7% by weight of the totalfertilizer composition; which provides a 42% by weight nitrogen (42N)contribution) is first coated with sulfur followed by a coating ofthermoset polymer (DEG-TEA polyol and diisocyanate, MDI) and a coatingof wax. The sulfur coating has a thickness achieved by a weightpercentage application of about 5% (55) based on the total weight of thegranule, a polymer layer of about 2.8 vvt % (2.8PU) based on the totalweight of the granule, and a wax layer of about 0.5 wt % (0.5W) based onthe total weight of the granule (shorthand descriptor:42N-5S-2.8PU-0.5W).

Example 2 42N-2.8PU-5S-0.5W (Comparative Example)

The urea granule (91.7% by weight of the total fertilizer compositionwhich provides a 42% by weight nitrogen (42N) contribution) has a firstcoating of thermoset polymer (DEA-TEG with MDI; composition as describedin Example 1), followed by a layer of sulfur and then followed by alayer of wax. The first polymer coating has a thickness achieved by aweight percentage application of about 2.8% (2.8PU) based on the totalweight of the granule, the sulfur layer of about 5% (5S) and wax layerof 0.5% (0.5W), either an intermediate wax, a paraffin wax, or analpha-olefin wax, based on the total weight of the granule (shorthanddescriptor: 42N2.8PU-5S-0.5W).

Example 3 43N-1.8PU-0.3W-3.8S-0.5W

In this Example, a controlled release fertilizer was prepared inaccordance with the present invention, however it is to be understoodthat other compositions may be prepared as described in the presentinvention.

The urea granule (93.6% by weight of the total fertilizer composition;which provides a 43% by weight nitrogen (43N) contribution) has a firstcoating of thermoset polymer (DEA-TEG with MDI; composition as describedin Example 1), followed by a layer of wax, followed by a layer of sulfurand then followed by a layer of wax. The polymer coating has a thicknessachieved by a weight percentage application of about 1.8% (1.8PU) basedon the total weight of the granule, the first wax layer of about 0.3%(0.3W), the sulfur layer of about 3.8% (3.8S) and wax layer of about0.5% (0.5W), either an intermediate wax, a paraffin wax, or analpha-olefin wax, based on the total weight of the granule (shorthanddescriptor: 43N-1.8PU0.3W-3.8S-0.5W).

Example 4 43N-2.8PU-0.3W-2.28-0.5W

In this Example, a controlled release fertilizer was prepared inaccordance with the present invention, however it is to be understoodthat other compositions may be prepared as described in the presentinvention.

The urea granule (94.5% by weight of the total fertilizer composition;which provides a 43% by weight nitrogen (43N) contribution) has a firstcoating of thermoset polymer (DEA-TEG with MDI; composition as describedin Example 1), followed by a layer of wax, followed by a layer of sulfurand then followed by a layer of wax. The polymer coating has a thicknessachieved by a weight percentage application of about 2.5% (2.5PU) basedon the total weight of the granule, the wax layer of about 0.3% 0.3W),the sulfur layer of about 2.2% (2.2S), and wax layer of about 0.5%(0.5W), either an intermediate wax, a paraffin wax, or an alpha-olefinwax, based on the total weight of the granule (shorthand descriptor:43N-2.8PU0.3W-2.2S-0.5W).

Example 5 Rate of Release of Nitrogen (N) from Controlled ReleaseFertilizer Compositions

The controlled release fertilizer compositions prepared in Example 1-4were tested for the rate of release of the fertilizer core before, andafter the impact test. The results of this test are shows in Table 1 andFIGS. 1A and 1B.

TABLE 1 % Nitrogen released of example compositions before and afterimpact test. % N released, cumulative 2 Hrs Day 1 Day 3 Day 7 Day 14 Day21 Cost Index Before Impact test (20° C.) Comparative Example 1 1.3 4.311 24 45 59.4 9.58 (42N—5S—2.8PU—0.5W) Comparative Example 2 0.38 1222.8 36.2 52.5 64.1 — (42N—2.8PU—5S—0.5W) Example 3 0.4 1.9 6.7 19.545.3 63.6 8.63 (43N—1.8PU—0.3W—3.8S—0:5W) Example 4 0.4 1.1 4.1 13.340.1 61 9.43 (43N—2.8PU—0.3W—2.2S—0.5W). After Impact Test (30° C.)Comparative Example 1 7.2 14.6 29 48 73.6 85 9.58 (42N—5S—2.8PU—0.5W)Comparative Example 2 6.1 17.5 35.8 54.4 73.2 83.5 — (42N—2.8PU—5S—0.5W)Example 3 1.5 7.9 21.5 42.2 70.2 83.7 8.63 (43N—1.8PU—0.3W—3.8S—0.5W)Example 4 1.1 5.2 12.5 30.9 63.7 81.3 9.43 (43N—1.8PU—0.3W—3.8S—0.5W)

As shown in Table 1, and FIGS. 1 and 2, controlled release fertilizerproducts described according to the present invention comprising a innerfertilizer core coated with, in series, a polymer layer, an intermediatelayer, a sulfur layer and an outer, water-insoluble layer such as43N-1.8PU-0.3W-3.8S-0.5W (Example 3) or 43N2.8PU-0.3W-2.2S-0.5W (Example4) exhibit a similar or slower fertilizer release rate (19.5% N releaseor 13.3% N release over 7 days, before impact test, or 42.2% and 30.9% Nrelease over 7 days after drop test) when compared to the prior artproduct, 42N-5S-2.8PU-0.5W (Example 1), that comprises more polyurethaneon a per weight basis (24% N release over 7 days before impact test, or48% N release after impact test).

The costs associated with production of the fertilizer products aredetermined by calculating the cost to produce the controlled releasefertilizer, including the cost of each component, and production andhandling costs to manufacture the product, expressed per unit nitrogenwithin the fertilizer product, to obtain a cost index. As indicated inTable 1, 43 N-1.8PU-0.3W-3.8S-0.5W (Example 3) has a cost index of 8.63,compared with a cost index of 9.58 for the prior art product 42N-5S-2.8PU0.5W (Example 1), or a cost index of 9.43 for43N-2.8PU-0.3W-2.2S-0.5W, Example 4.

All citations are hereby incorporated by reference.

The present invention has been described with regard to one or moreembodiments. However, it will be apparent to persons skilled in the artthat a number of variations and modifications can be made withoutdeparting from the scope of the invention as defined in the claims.

The invention claimed is:
 1. A controlled release fertilizercomposition, comprising: a) a core comprising one or more plant nutrientmaterials; b) a polymer layer coating the core, wherein the polymerlayer comprises a polymer formed on the core from two or more precursorcompounds; c) a sulfur layer overlying the polymer layer; d) anintermediate layer between the polymer layer and the sulfur layer,wherein the intermediate layer functions as a lubricant when applyingthe sulfur layer; and e) optionally an outer, water-insoluble layer. 2.The control release fertilizer of claim 1, wherein the core comprisesnitrogen, phosphorus, potassium, sulfur, micronutrients or mixturesthereof.
 3. The controlled release fertilizer of claim 1, wherein thecore comprises urea.
 4. The controlled release fertilizer of claim 1,wherein the precursor compounds comprise an isocyanate and a polyol. 5.The controlled release fertilizer of claim 4, wherein the isocyanatecomprises a diisocyanate.
 6. The controlled release fertilizer of claim4, wherein the isocyanate comprises a polyisocyanate.
 7. The controlledrelease fertilizer of claim 4, wherein the isocyanate comprises 4,4diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate,2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4′-diphenylmethanediisocyanate, or 4,4′-diphenylmethanie diisocyanate.
 8. The controlledrelease fertilizer of claim 1, wherein the precursor compounds comprisea polyol.
 9. The controlled release fertilizer of claim 8, wherein thepolyol comprises a glycol.
 10. The controlled release fertilizer ofclaim 8, wherein the polyol comprises diethylene glycol polyol,orthophathalate diethylene glycol based polyester polyols,terephthalate-diethylene glycol based polyester polyols, castor oil,oils modified to contain amine or OH groups comprising modified tungoil, soybean oil, canola oil, sunflower oil, or linseed oil,oleo-polyols comprising epoxidized castor oil, epoxidized sunflower oil,or epoxidized linseed oil, polyether polyols, castor oil derivativescomprising partial hydrolysates of castor oil formed by reacting castoroil with a polyol selected from diols comprising ethylene glycol ordipropylene glycol, or esters formed by reactions between ricinoleicacid and ethylene glycol, or dipropylene glycol.
 11. The controlledrelease fertilizer of claim 1, wherein the precursor compounds comprisea polyol and a polyisocyanate and the polymer comprises a polyurethane.12. The controlled release fertilizer of claim 1, wherein the precursorcompounds comprise MDI and DEG-TEA polyol.
 13. The controlled releasefertilizer of claim 1, wherein the intermediate layer is a wax.
 14. Thecontrolled release fertilizer of claim 13, wherein the wax comprisesintermediate petroleum wax, alpha olefin wax, polyethylene wax, paraffinwax, silicon wax, slack wax, microcrystalline wax, or natural wax. 15.The controlled release fertilizer of claim 13, wherein the wax comprisesintermediate petroleum wax, paraffin wax, or polyolefin wax.
 16. Thecontrolled release fertilizer of claim 1, wherein the one or more plantnutrients are about 37%-44% N on a weight basis, the polymer is about1.2%-3.0% on a weight basis, the intermediate layer is about 0.1%-0.8%on a weight basis, the sulfur layer is about 1.7%-15% on a weight basisand the optional outer layer is about 0.1%-0.8% on a weight basis.
 17. Acontrolled release fertilizer composition, comprising: a) a corecomprising one or more plant nutrient materials; b) a thermoset polymerlayer coating the core, wherein the thermoset polymer layer is fromprecursor compounds comprising MDT and DEG-TEA polyol; c) a sulfur layeroverlying the polymer layer; d) an intermediate wax layer coated betweenthe polymer layer and the sulfur layer, wherein the intermediate layercomprises an alpha olefin wax that functions as a lubricant whenapplying the sulfur layer; and e) optionally an outer, water-insolublelayer.
 18. A method of producing a controlled release fertilizercomposition, comprising the steps of: a) coating one or more plantnutrient materials with two or more precursor compounds under conditionseffective to form a polymer layer coating a core comprising the one ormore plant nutrient materials; b) coating a lubricant onto the polymerlayer; c) applying molten sulfur onto the lubricant under conditionseffective to form a sulfur layer comprising solidified sulfur; and d)optionally applying an outer layer onto the sulfur layer.
 19. The methodof claim 18, wherein the one or more plant nutrients comprise urea. 20.The method of claim 18 wherein the lubricant comprises intermediatepetroleum wax, alpha olefin wax, polyethylene wax, paraffin wax, siliconwax, slack wax, microcrystalline wax, or natural wax.
 21. The method ofclaim 18, wherein the two or more than two precursor compounds are apolyisocyanate and a polyol and the step of coating the one or moreplant nutrients with two or more than two precursor compounds reactiveto form a polymer is at a temperature sufficient to form a polyurethanepolymer.
 22. The method of claim 18, wherein the one or more plantnutrients are about 37%-44% N on a weight basis, the thermoset polymeris about 1.2%-3.0% on a weight basis, the lubricant is about 0.1%-0.8%on a weight basis, the sulfur is about 1.7%-15% on a weight basis andthe optional outer layer is about 0.1%-0.8% on a weight basis.
 23. Amethod of producing a controlled release fertilizer composition,comprising the steps of: a) coating a lubricant onto a particlecomprising a polymer layer that coats a core comprising at least oneplant nutrient material; b) coating molten sulfur onto the lubricantunder conditions such that the lubricant helps the molten sulfur form amore uniform sulfur coating comprising solidified sulfur.
 24. A methodof producing a controlled release fertilizer particle comprising thesteps of: a) coating one or more plant nutrients with two or more thantwo precursor compounds reactive to form a polyurethane polymer layer;b) applying a lubricant onto the polymer layer; c) spraying moltenelemental sulfur onto the lubricant to form a sulfur layer; and d)applying a wax layer onto the sulfur layer to form the controlledrelease fertilizer particle.
 25. The controlled release fertilizer ofclaim 24, wherein the lubricant comprises a component selected from thegroup consisting of a wax, an oil, a lubricant, a surfactant, and acombination thereof.
 26. The controlled release fertilizer of claim 25,wherein the lubricant comprises a wax.
 27. The controlled releasefertilizer of claim 26, wherein the lubricant comprises intermediatepetroleum wax, alpha olefin wax, polyethylene wax, paraffin wax, siliconwax, slack wax, microcrystalline wax, or natural wax.
 28. The controlledrelease fertilizer of claim 24, wherein the wax layer comprisesintermediate petroleum wax, alpha olefin wax, polyethylene wax, paraffinwax, silicon wax, slack wax, microcrystalline wax, or natural wax.